%0 Journal Article
%A Donzello, Maria Pia
%A Ercolani, Claudio
%A Chiesi-Villa, Angiola
%A Rizzoli, Corrado
%D 1998
%T One Step Forward to “Stapled” Bis(phthalocyanine) Metal Complexes: Synthesis,
Characterization, and Redox Properties of Bis(phthalocyaninato)niobium(IV). X-ray
Crystal Structure of the Monoelectronically Oxidized Species [Pc2Nb](I3)(I2)0.5(ClNP)3.5
(ClNP = 1-Chloronaphthalene)
%U https://acs.figshare.com/articles/journal_contribution/One_Step_Forward_to_Stapled_Bis_phthalocyanine_Metal_Complexes_Synthesis_Characterization_and_Redox_Properties_of_Bis_phthalocyaninato_niobium_IV_X-ray_Crystal_Structure_of_the_Monoelectronically_Oxidized_Species_Pc_sub_2_sub_Nb_I_sub_3_sub_I_sub_2_sub_su/3619851
%R 10.1021/ic970841f.s002
%2 https://acs.figshare.com/ndownloader/files/5708478
%K Pc 2 Nb
%K C 11A
%K Step Forward
%K saltlike species
%K UV
%K C 31A
%K Redox Properties
%K Monoelectronically Oxidized Species
%K ClNP
%X Bis(phthalocyaninato)niobium(IV) has
been prepared and isolated as a monosolvate,
[Pc2Nb]·ClNP (ClNP =
1-chloronaphthalene). It is a light-brown, stable-to-air
Nb(IV) (d1) paramagnetic sandwich-like species,
which,
upon oxidation by I2 under mild conditions, undergoes a
metal-centered monoelectronic oxidation to give the
diamagnetic Nb(V) (d0)
[Pc2Nb]+ fragment, with formation of
saltlike species of formula
[Pc2Nb](I3)(I2)0.5(ClNP)3.5 (I). The structure of I
has been elucidated by single-crystal X-ray work. Crystals are
triclinic: formula
C64H32N16Nb·I3·0.5I2·3.5C10H7Cl,
M = 2194.8, a = 17.702(3) Å,
b = 18.708(3) Å, c = 13.504(2) Å,
V = 4267.5(13) Å3, α = 106.00(2)°, β =
93.39(2)°, γ = 83.26(1)°, Z = 2, space
group P1̄. The structure of the
[Pc2Nb]+
fragment, “stapled” by two inter-ligand C−C σ bonds
(C11A−C11B and C31A−C31B = 1.574(15) Å),
together
with its color and UV−visible spectral behavior, allows a
straightforward assignment of the same “stapled”
structure
to the unoxidized [Pc2Nb]. The present niobium
sandwiched materials reiterate the peculiar structural
findings
shown only by the previously reported
[Pc2Ti].
%I ACS Publications